KR101499766B1 - Water- and oil-repellent coating film and articles having this coating film - Google Patents

Abstract

(assignment)
An object of the present invention is to provide a coating film which can more reliably obtain excellent water repellency and oil repellency.
(Solution)
(1) the coating film contains a metal oxide composite particle, and (2) the metal oxide composite particle is a composite oxide of a) metal oxide particles and b (3) the fluorine content (% by weight) of the metal oxide composite particle is divided by the surface area (m ² / g) of the metal oxide particle, and the coating layer containing the polyfluoroalkyl methacrylate resin Water-repellent coating film having a value of 0.025 to 0.180.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a water-repellent, oil-repellent coating film,

The present invention relates to a water-repellent / oil-repellent coating film (water-repellent / oil-repellent coating film) and an article comprising the coating film.

Various articles such as structures, textiles, and toys are known in addition to the packaging materials (containers, wrapping paper, trays, tubes, bags, pouches, etc.) For example, in packaging materials, foods, beverages, medicines, cosmetics such as jelly sweets, puddings, yogurt, liquid detergents, cream toothpaste, curry roux, syrup, vaseline, facial cream, , And chemical materials. In addition, the content of the contents may be various kinds such as solid, semisolid, liquid, viscous substance, gel substance and the like. Water repellency or oil repellency is imparted to the surface of the contents to be contacted, depending on the kind of the contents, so that the contents are not adhered as much as possible.

As a means for imparting water repellency and oil repellency, for example, a method of coating a fluorine compound or the like is used.

For example, Patent Document 1 discloses a thermoplastic resin layer (A), a perfluoroalkyl group (perfluoroalkyl group), a perfluoroalkyl group (perfluoroalkyl group) (Oil-resistant paper) B comprising an oil resistance agent having a carbon number of less than 8 and a back surface opening y having a diameter of 0.2 to 0.6 mm (Oil-resistant packaging material) in which at least three layers of a heat sealable thermoplastic resin layer (C) are laminated in this order.

Patent Document 2 discloses a water and oil repellent base material comprising a first layer formed on a surface of a base material and a second layer formed on a surface of the first layer, A layer formed of a cured product (cured product) of a curable coating material containing fine silica particles, a layer formed of a composition containing a fluorosilicone compound and a solvent as essential components as a second layer, or a layer formed of a cured product of the above- Has been proposed.

Patent Document 3 discloses a method in which a urethane-based or vinyl chloride-based transparent ink using an isocyanate-based curing agent is first coated on at least one surface of an air permeable paper base material, An antioxidant, an ethanol evaporating agent or a hygroscopic agent for maintaining the freshness of a food characterized by a two-layer coating comprising a fluorinated water-repellent oil-repellent coating on a vinyl chloride-based transparent acrylic ink layer, (Absorbing agent) is disclosed.

As a technique for coating such a fluorine-based compound, a method of coating a dispersion (dispersion) containing fine particles and a oil-repellent agent has also been proposed.

For example, Patent Document 4 discloses a method of producing fine particles having a particle diameter of 100 nm or more by (1) sol-gel method, and (i) immersing the coated article in a dispersion in which the fine particles are dispersed (I) a first step of spraying and drying a dispersion liquid in which the fine particles are dispersed, (ii) a step of spraying the fine particles and the oil repellent agent having a particle diameter of 7 to 90 nm Immersing, lifting and drying the coated article in a dispersion containing perfluoro alkylsilane as a solvent and / or (ii) dispersing the dispersion containing fine particles and a oil-repellent agent having a particle diameter of 7 to 90 nm into the coated article And a second step of spraying and drying the oil-repellent coated article.

Patent Document 5 discloses a coated article obtained by coating a coating composition comprising alcohol, alkoxysilane, perfluoroalkylsilane, silica fine particles, a catalyst for promoting the hydrolysis reaction of alkoxysilane, and water, (RMS) value of 100 nm or more on the surface of a water-repellent or oil-repellent coating material.

Japanese Unexamined Patent Application Publication No. 2011-73744 Japanese Patent Application Laid-Open No. 2000-169835 Japanese Patent Application Laid-Open No. 2009-191407 Japanese Unexamined Patent Application Publication No. 2011-140625 Japanese Patent Application Laid-Open No. 2010-89373

However, in the techniques described in these patent documents, water repellency or oil repellency has been achieved to a certain extent. However, in advancing practical use, it is necessary to find a method for more surely realizing sufficient water repellency and oil repellency.

Therefore, a main object of the present invention is to provide a coating film which can more reliably obtain excellent water repellency and oil repellency.

The inventor of the present invention has made intensive studies in view of the problems of the prior art, and as a result, it has been found that the above object can be achieved by employing a coating film containing specific particles, and the present invention has been accomplished.

That is, the present invention relates to the following water repellent / oil repellent coating film.

1. A coating film formed on the surface of a material for imparting water repellency and oil repellency,

(1) The coating film contains metal oxide composite particles,

(2) The metal oxide composite particle includes a) a metal oxide particle, and b) a coating layer comprising a polyfluoroalkyl methacrylate resin formed on the surface thereof,

(3) A water- and oil-repellent coating film characterized in that the value obtained by dividing the fluorine content (wt%) of the metal oxide composite particle by the surface area (m ² / g) of the metal oxide particle is 0.025 to 0.180.

2. The water- and oil-repellent coating film according to item 1, wherein the value obtained by dividing the carbon content (wt%) of the metal oxide composite particle by the surface area (m ² / g) of the metal oxide particle is 0.05 to 0.400.

3. The water- and oil-repellent coating film according to item 1 or 2 above, wherein the average primary particle size of the metal oxide particles is 5 to 50 nm.

4. The water- and oil-repellent coating film according to any one of items 1 to 3, wherein the metal oxide particles are at least one of silicon oxide particles, aluminum oxide particles and titanium oxide particles.

5. The water- and oil-repellent coating film according to any one of items 1 to 4, wherein the coating layer contains no silicon component.

6. The water- and oil-repellent coating film according to any one of items 1 to 5, wherein the coating film is porous.

7. The water- and oil- repellent coating film according to any one of items 1 to 6, wherein the coating film surface which is the outermost surface has a concavo-convex structure formed by the metal oxide composite particles.

8. The water- and oil-repellent coating film according to any one of items 1 to 7, wherein the content of the metal oxide composite particles in the coating film is 10 to 100% by weight.

9. The water- and oil-repellent coating film according to any one of items 1 to 8, wherein the coating film further comprises an adhesive component.

10. A packaging material comprising the water- and oil-repellent coating film according to any one of items 1 to 9 above.

11. The packaging material according to item 10 above, which comprises the water-repellent / oil-repellent coating film, the heat seal layer and the base material layer according to any one of items 1 to 9 in this order.

12. The packaging material according to item 11 above, wherein part or all of the water- and oil-repellent coating film present on the area to be the heat seal is embedded in the heat seal layer at the time of heat sealing.

13. The water- and oil-repellent coating film according to any one of items 1 to 9, which is a coating film obtained by a method comprising a step of coating a surface of a material with a dispersion liquid in which the metal oxide composite particles are dispersed.

14. A method of making a package product in which the contents are filled in a container,

(1) a step of charging the contents into the container,

(2) A process of sealing the contents by using the packaging material of the above item 11 as a lid material and heat-sealing the water-repellent / oil-repellent coating film of the packaging material while contacting the container opening

Comprising the steps of:

15. The production method according to the above-mentioned Item 14, wherein part or all of the water-repellent / oil-repellent coating film present on the region where the packaging material is heat-sealed is embedded in the heat seal layer at the time of heat sealing.

16. The production method according to item 14 above, wherein the area where the packaging material is heat-sealed is exposed to the heat seal layer because no water repellent / oil repellent coating film is formed.

17. The production method according to any one of items 14 to 16, wherein the contents have fluidity.

18. The production method according to any one of items 14 to 17, wherein the content is a liquid.

19. The production process according to any one of items 14 to 18, wherein the content comprises water and / or an oil component.

20. The production method according to any one of items 14 to 19, wherein the content of the content at 20 캜 is 0.01 to 500 dPa..

According to the present invention, it is possible to provide a coating film which can more reliably obtain excellent water repellency and oil repellency by using the metal oxide composite particle having a specific coating layer. Particularly, when fine and complex irregularities are formed on the surface of the coating film by continuous operation of a plurality of metal oxide composite particles, the synergistic action of the irregular structure and the coating layer leads to better water repellency and oil repellency Can be achieved.

The coating film having these characteristics can be suitably used for packaging materials, dishes, cooking utensils, kitchen utensils, daily necessities, clothes, building products, structures, transportation equipment and the like. In particular, it can be suitably used as a packaging material, such as a lid material, for example, a molded container, a wrapping paper, a tray, a tube, a bag, a pouch and the like. When used as a packaging material, the contents may include water and / or oily liquids. That is, contents having fluidity can be applied. More specifically, in addition to foods such as curry, stew, yogurt, jelly sweets, puddings, seasonings (for example, broth, dressing, etc.), liquid detergents, paste toothpaste, facial cleanser, Cosmetics, medicines, and the like.

1 is a schematic diagram of the metal oxide composite particle of the present invention.
2 is a schematic diagram of a coating film of the present invention.
Fig. 3 is a view showing the layer structure of the packaging material including the coating film of the present invention. Fig.
4 is a view showing the result of observing the surface of the coating film of Example 2-4.

The water repellent / oil repellent coating film (water repellent / oil repellent coating film) of the present invention is a coating film formed on the surface of a material for imparting water repellency and oil repellency,

(1) The coating film contains metal oxide composite particles (metal complex oxide particles)

(2) The metal oxide composite particle includes a coating layer (coating layer) comprising a) metal oxide particles and b) a polyfluoroalkyl methacrylate resin formed on the surface thereof,

(3) The value obtained by dividing the fluorine content (% by weight) of the metal oxide composite particle by the surface area (surface area) (m ² / g) of the metal oxide particle is 0.025 to 0.180.

Fig. 1 shows a schematic diagram of a metal oxide composite particle. As shown in Fig. 1, the metal oxide composite particle 11 includes metal oxide particles 13 serving as a core and a coating layer 12 formed on the surface thereof. The metal oxide particles 13 forming the core form an aggregate structure (aggregated porous structure) in which a plurality of metal oxide particles (primary particles) are three-dimensionally continuous. The coating layer 12 is formed in the inside of the aggregate structure and in the shell. In Fig. 1, this aggregate structure is schematically represented by a sphere, and the coating layer 12 is shown only on the outer periphery. Fig. 2 shows a schematic diagram of the coating film 21 including the metal oxide composite particles 11. Fig. The coating film 21 is formed on the surface of the material 22 and includes a metal oxide composite particle 11 and a void 23 formed between the metal oxide composite particle 11 and the particle. It is preferable that the surface 24 (outermost surface) of the coating film 21 forms a concavo-convex structure (concavo-convex structure) (concavo-convex surface) by a plurality of metal oxide composite particles 11. That is, in the coating film of the present invention, it is preferable that the surface of the coating film is provided with the concavo-convex structure by the metal oxide particles in order to obtain higher water repellency and oil repellency.

The coating layer 12 including the polyfluoroalkyl methacrylate resin formed on the surface of the metal oxide composite particle 11 and the irregular surface 24 interact with each other to exhibit high water repellency and oil repellency. In addition, since the coating film of the present invention is covered with the covering layer 12 containing a predetermined amount of the polyfluoroalkyl methacrylate resin, all of the metal oxide composite particles contained therein are uniformly distributed over the entire surface of the coating film surface Water repellency and oil repellency can be obtained. In other words, since each of the metal oxide composite particles has the coating layer 12 in an amount sufficient to exhibit high water repellency and oil repellency, the water repellency and oil repellency are exhibited without spots throughout the coating film. As a result, Water repellency and oil repellency can be imparted to the material 22.

In the coating film of the present invention, even if there is a substance (particularly an aqueous or oily liquid) to be attached to the outermost surface of the coating film, the substance is repelled by its water repellency and oil repellency, It is possible to prevent the substance from adhering to the substrate 21.

1. Materials

The material forming the coating film of the present invention (that is, the material to which water repellency and oil repellency are imparted) is not particularly limited. The material may be, for example, metal, plastic, ceramics, rubber, a fibrous material (paper, nonwoven fabric, fabric, etc.), or a composite material thereof. It may also be a product, a semi-finished product, or a raw material thereof.

(Roof, wallpaper, flooring, ceiling material, tile, window glass, etc.) other than the packaging material (packaging material) Kitchen utensils, sporting goods, clothing (hat, shoes, gloves, coats, etc.), structures (such as cooking utensils, cooking utensils, And can be widely applied to cosmetics, medicines, toys, and sensing jigs, for example, in the case of a car, a wall, a bridge, a tower, and the like), transportation equipment (such as a car, a bike,

In the present invention, a packaging material is particularly suitable as the above-mentioned material. The packaging material also includes both a package as a product (finished product) and its raw materials. Examples of the product (finished product) include a lid of the container, and a package such as a molded container, a wrapping paper, a tray, a tube, a jaruche (pouch, etc.). Examples of raw materials for the package include a laminate including a base material and a heat seal layer. That is, a packaging material (the packaging material of the present invention) provided with the water-repellent / oil-repellent coating film, the heat seal layer and the base material layer of the present invention in this order. Hereinafter, an embodiment as a representative example of the packaging material of the present invention is shown.

2. Coating film

The coating film according to the present invention includes metal oxide composite particles. The content of the metal oxide composite particles in the coating film can be appropriately set according to the desired water repellency, oil repellency, etc., but it is usually from 10 to 100 wt%, particularly preferably from 30 to 100 wt%. That is, in the present invention, when the content of the metal oxide composite particles is close to 100% by weight, water repellency and oil repellency as high as that can be obtained.

The amount of the coating film applied to the material (weight after drying) is not limited, but may be suitably set according to the desired water repellency, oil repellency, content of the metal oxide composite particles, etc., but is usually 0.01 to 30 g / m ² , It can be set within a range of 30 g / m ² . Therefore, it may be suitably set in the range of about ¹ to 30 g / m ² , particularly in the range of ² to 8 g / m ² .

1) Metal oxide composite particles and its preparation (Preparation)

1-1) Metal oxide composite particles

The metal oxide composite particle includes a) a metal oxide particle, and b) a coating layer comprising a polyfluoroalkyl methacrylate resin formed on the surface thereof.

The metal oxide particle according to a) is not limited as long as it can be a core of the metal oxide composite particle. For example, at least one of particles (powder) such as silicon oxide, titanium oxide, aluminum oxide, Can be used. In the present invention, at least one of silicon oxide particles, titanium oxide particles and aluminum oxide particles is particularly preferable. These metal oxide particles themselves may be known or commercially available ones. In addition, the average primary particle diameter of the metal oxide particles is not limited, but is preferably 5 to 50 nm, particularly preferably 7 to 30 nm. By setting the particle diameter within the range of the particle diameter, better water repellency and oil repellency can be obtained.

The average primary particle diameter of the metal oxide particles in the present invention can be measured by using a transmission electron microscope or a scanning electron microscope. More specifically, the average primary particle diameter can be obtained by photographing with a transmission electron microscope or a scanning electron microscope, measuring the diameter of 200 or more particles on the photograph, and calculating the arithmetic mean value.

The nano-level metal oxide particles may be those known or commercially available. AEROSIL 300, AEROSIL 50, AEROSIL 200FAD, and AEROSIL 380 (both of which are trade names of AEROSIL 200, AEROSIL 130, AEROSIL 300, , Manufactured by NIPPON AEROSIL CO., LTD.), And the like. Examples of the titanium oxide include AEROXIDE TiO ₂ T805 (product of EVONIK JAPAN CO., LTD.) And the like. As the aluminum oxide, for example, the product name "AEROXIDE Alu C 805" (product of Ebonic Degussa) can be mentioned.

The coating layer relating to b) above includes a polyfluoroalkyl methacrylate resin. By using the resin, it is possible to form a strong coating layer having a relatively high adhesion on the surface of the particles because of its excellent affinity with the metal oxide particles (particularly, the silicon oxide particles), and also to exhibit high water repellency and oil repellency . Such a resin itself may be a known or commercially available resin. As a commercial product, for example, a product name "CHEMINOX FAMA C-6" (product of UNIMATEC CO., LTD. (Japan)), product name "Zonyl TH Fluoromonomer code 421480" (SIGMA- SCFC-65530-66-7 (product of Maya High Purity Chem (CHINA)), product name "FC07-04 ~ 10" (available from Aldrich Chemical Co., (Product of Wilshire Chemical Co., Inc (USA)), product name " AsahiGuard AG-E530 " (trade name) available from Fluory, Inc. TEMA-N "(a product of Top Fluorochem Co., LTD (CHINA), China)," Asahi Glass AG-E060 "(all available from ASAHI GLASS Co., The product name "Zonyl 7950" (product of SIGMA-RBI (SWITZ), Switzerland), product name "6100840-6100842" (Manufactured by Weibo Chemcal Co., Ltd. (CHINA)) and CB INDEX: 75 (ABCR GmbH & CO.KG (GERMANY), Germany).

Among them, a) polyfluorooctyl methacrylate, b) 2-N, N-diethylaminoethyl methacrylate (hereinafter referred to as " N, N-diethylaminoethyl methacrylate, c) 2-hydroxyethyl methacrylate, and d) 2,2'-ethylenedioxydiethyl dimethacrylate. Can be suitably employed as the above-mentioned resin. They may also use commercially available products as described above.

In the present invention, the value (A value) obtained by dividing the fluorine content (% by weight) of the metal oxide composite particles by the surface area (m ² / g) of the metal oxide particles is 0.025 to 0.180, preferably 0.030 to 0.175 . The value (B value) obtained by dividing the carbon content (% by weight) of the metal oxide composite particle by the surface area (m ² / g) of the metal oxide particle is 0.05 to 0.400, particularly preferably 0.06 to 0.390. The carbon content and the fluorine content are indicative of the degree of coating in the present invention, and the larger the numerical value, the greater the coating amount. In the present invention, good adhesion to the surface of metal oxide particles, excellent water repellency and oil repellency can be achieved by setting the coating amount (carbon content and fluorine content, in particular, fluorine content). If the value obtained by dividing the fluorine content (% by weight) by the surface area (m ² / g) of the metal oxide particles is less than 0.025, desired water repellency and oil repellency can not be obtained. When the value obtained by dividing the carbon content (% by weight) by the surface area (m ² / g) of the metal oxide particles is less than 0.05, desired water repellency and oil repellency may not be obtained. On the other hand, if the value obtained by dividing the fluorine content (% by weight) by the surface area (m ² / g) of the metal oxide particles exceeds 0.180, the production of the metal oxide composite particles becomes difficult. Further, when the value obtained by dividing the carbon content (wt%) by the surface area (m ² / g) of the metal oxide particles is more than 0.400, it sometimes becomes difficult to produce the metal oxide composite particles. Therefore, in the present invention, in order to achieve an excellent water repellency and oil repellency, the value of A is preferably set within a predetermined range, and in order to realize better water repellency and oil repellency, the B value is also preferably set within a predetermined range.

In the measurement of the carbon content in the metal oxide composite particles in the present invention, the carbon contained in the hydrophobic group on the surface is changed to CO ₂ by heating the sample (analyte) in an oxygen atmosphere at 800 ° C or higher , And calculating the carbon content present on the surface of the specimen by a trace carbon analyzer. The fluorine content in the metal oxide composite particles of the present invention can be obtained by recovering the gas produced by firing the specimen in a ring furnace at 1000 캜 by steam distillation, Fluorine ion is detected and quantified. The surface area (m ² / g) (specific surface area) was determined by the BET one-point method using Macsorb (manufactured by MOUNTECH CO., LTD., Japan). The adsorption gas used was 30% by volume of nitrogen and 70% by volume of helium. As pretreatment of the sample, adsorption gas was circulated for 10 minutes at 100 ° C. Thereafter, the cell containing the sample was cooled by liquid nitrogen, and the surface area of the sample was obtained from the amount of nitrogen removed by raising the temperature to room temperature after completion of adsorption. The specific surface area was determined by dividing by the mass of the sample.

1-2) Preparation of metal oxide composite particles

The method of preparing the metal oxide composite particle is not particularly limited and may be a method in which a polyfluoroalkyl methacrylate resin is used as a coating material for the metal oxide particles (powder), and the coating method, the granulation method The coating layer may be formed. For example, a step of coating a coating liquid obtained by dissolving or dispersing a liquid polyfluoroalkyl methacrylate resin in a solvent onto a particle of a metal oxide (coating step) Can be suitably prepared.

As the polyfluoroalkyl methacrylate resin in the above-mentioned production method, a liquid phase liquid at normal temperature (25 DEG C) and atmospheric pressure can be suitably used. As the polyfluoroalkylmethacrylate resin, commercially available products exemplified above may be used.

The solvent used for the coating liquid is not particularly limited, and in addition to water, organic solvents such as alcohol and toluene can be used. In the present invention, water is preferably used. That is, it is preferable to use a coating liquid in which a polyfluoroalkyl methacrylate resin is dissolved and / or dispersed in water as a coating liquid.

The content of the polyfluoroalkylmethacrylate resin in the coating liquid is not particularly limited, but is generally 10 to 80% by weight, particularly 15 to 70% by weight, more preferably 20 to 60% by weight .

For example, the spraying method, the dipping method, and the stirring and granulating method (stirring granulation method) are all applied to the method of coating the surface of the metal oxide particles with the coating liquid, can do. Particularly, in the present invention, a coating by a spray method is particularly preferable because it is excellent in uniformity and the like.

After coating the coating liquid, the solvent is removed by heat treatment to obtain the metal oxide composite particles. The heat treatment temperature is usually about 150 to 250 占 폚, particularly preferably 180 to 200 占 폚. The atmosphere of the heat treatment is not limited, but an inert gas (non-oxidizing atmosphere) such as nitrogen gas or argon gas is preferable. Further, for example, if necessary, a series of steps including a coating step and a heat treatment step can be carried out one or more times. This makes it possible to appropriately control the coating amount and the like.

2) Other components in the coating film

The coating film of the present invention may contain other components in addition to the above-mentioned metal oxide composite particles within the range not hindering the effect of the present invention. For example, adhesives (heat seal agents and the like), colorants, dispersants, anti-settling agents, viscosity adjusting agents, and printing protectants.

In particular, it is effective to contain an adhesive (adhesive component) in order to further increase the adhesion strength of the coated film to the article and the adhesion strength between the metal oxide composite particles, depending on the kind of the article to which the coating film of the present invention is applied. The adhesive that can be used in this case is not particularly limited, and known or commercially available adhesives can be used. (For example, a heat seal agent) such as a polyolefin resin, a polyester resin, a polyurethane resin, an epoxy resin, an acrylic resin and a vinyl resin. As the heat seal agent, more specifically, low density polyethylene, medium density polyethylene, high density polyethylene, linear (linear) low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene - polyolefin resins such as acrylic acid polymers, ethylene-ethyl acrylate copolymers, ethylene-methacrylic acid polymers, ethylene-methyl methacrylate copolymers, ethylene-propylene copolymers, methylpentene polymers, polybutene polymers, polyethylene or polypropylene Modified polyolefin resin modified by an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid or itaconic acid, polyvinyl acetate resin, poly (meth) acrylic resin, polyacrylonitrile resin , Polyvinyl chloride resin, other thermally adhesive resin The resin blends thereof, copolymers comprising a combination of monomers constituting them, a modified resin and the like can be used as a heat ssilje.

In the case of using the heat seal agent, for example, in the "3. Method of forming a coating film" described later, the heat seal agent particles (powder) are coated with a dispersion in which the metal oxide composite particles are dispersed, By applying the heat seal agent in the heat treatment step in " 3. Method for Forming Coating Film ", it is possible to form a coating film having better adhesion with the material surface. In the case of using an adhesive, the content of the adhesive in the coating film may be suitably set so as to be usually in the range of 20 to 80% by weight in the coating film.

3. Method for forming coating film

The method for forming the coating film of the present invention is not particularly limited, and a known method and the like can be applied. Particularly in the present invention, a coating film can be suitably formed by a method including a step of coating a dispersion liquid containing metal oxide composite particles on the surface of a material. That is, after coating with a wet process, the solvent is removed to obtain a water- and oil-repellent coating film. In the case of using perfluoro alkylsilane as the fluorine-based water and oil repellent of the prior art, the pH of the water-containing emulsion is adjusted by adding a catalyst or controlling the hydrolysis reaction of the alkoxysilane group With respect to what is necessary, in the present invention, a desired coating film can be relatively easily formed without such a process. If the solvent used is water, the load on the environment can be minimized.

The solvent used in the dispersion is not particularly limited and includes, for example, water, alcohols such as alcohol (ethanol), cyclohexane, toluene, acetone, IPA, propylene glycol, hexylene glycol, butyldiglycol, pentamethylene glycol, N-hexane, hexyl alcohol, and the like.

The dispersion amount of the metal oxide composite particles relative to the organic solvent can be suitably determined within a range of usually about 20 to 50 g / L (liter), depending on the kind of the material, the water repellency and the degree of oil repellency.

Further, as shown in the other components in the above (2) coating film, an adhesive (particularly, a heat seal agent) may be contained in the dispersion. More specifically, particles of the adhesive component can be dispersed in the dispersion. As the adhesive component, those shown in the other components in the above (2) coating film can be used. In addition to these, components other than those shown in the "other components in the coating film (2)" may be contained in the dispersion.

The method of coating the dispersion on the surface of the material is not limited, and a known method can be employed. Such as roll coating, gravure coating, bar coat, doctor blade coating, comma coater, part coat, brush coating and the like can all be adopted.

The amount of coating of the dispersion liquid is not limited, and the weight of the metal oxide composite particle after drying of the coating film is appropriately set within a range of, for example, 0.01 to 30 g / m ² , preferably 0.1 to 30 g / m ² . Thus, for example, it may be adjusted such that the 50~600mg / m ² or so, especially 200~500mg / m ^2.

The dispersion may be coated on the surface of the material and then dried. The drying may be natural drying or heat drying. In the case of heating and drying, it is usually sufficient to heat to 200 ° C or lower, preferably 100 ° C or lower.

In the present invention, after the dispersion liquid is coated on the surface of the material, a heat treatment step may be performed after the drying step or in place of the drying step. In particular, in the case where the dispersion contains a heat sealant as an adhesive component, the heat seal agent is melted by heat treatment of the coating film on the surface of the material, so that the coating film can be firmly fixed to the surface of the material. As a result, it is possible to form a coating film in which peeling and dropout are less likely to occur. The heat treatment temperature may be appropriately set depending on the type of the heat seal agent to be used and the like, but it is usually within a range of about 150 to 250 캜. The atmosphere of the heat treatment is not limited, but it may be usually in the air or in an oxidizing atmosphere.

4. Properties of the coating film

The water-repellent and oil-repellent coating film of the present invention includes metal oxide composite particles, but it is particularly preferable that the surface of the coating film has a concavo-convex structure (approximate fractal structure) formed by metal oxide composite particles. More specifically, it is preferable that the metal oxide composite particles have a void formed by continuous contiguous particles and a surface formed by the particle body. Accordingly, the metal oxide composite particle has a predetermined coating layer and can exhibit better water repellency and oil repellency. That is, the surface of the concavo-convex structure is substantially constituted by the coating layer, the water repellency and the oil repellency can be further improved. In this case, the particles contributing to the formation of the concavo-convex structure may include those other than the metal oxide composite particles within a range not hindering the effect of the present invention. The concavo-convex structure on the surface of the coating film can be observed with a scanning electron microscope. The embodiment 2-4 to be described later is shown in Fig. 4 as a representative example.

The thickness of the coating film is not particularly limited, but may be suitably determined within a range of usually 0.5 to 30 mu m. Particularly, in the case of a construction in which the coating film is embedded in the heat seal layer at the time of heat sealing as the packaging material, the thickness is preferably set to about 1 to 8 mu m.

The water repellency of the coating film is preferably a contact angle of pure water (25 ° C) of at least 140 degrees, particularly at least 150 degrees. As for oil repellency, it is preferable that the contact angle of cooking oil: olive oil (25 DEG C) is 130 DEG C or more, particularly 140 DEG C or more. Further, the fall angle (drop angle) (olive oil) of the coating film is not limited, but is preferably 5 to 20 degrees.

≪ Embodiment of packaging material of the present invention >

Hereinafter, an embodiment will be described in which a packaging material is produced by using a laminate including a sheet-like base material and a heat seal layer as the material of the above item 1. [ 3, a coating film 21 is formed as an outermost layer on a layered product 34 in which a heat seal layer 32 is laminated so as to be in contact with the sheet-like base material 33, as shown in Fig.

a) Composition of laminate

As the sheet-like base material 33, a known material can be employed. For example, a single piece of paper, a synthetic paper, a resin film, a resin film with a vapor deposition layer (vapor deposition layer-attached resin film), an aluminum foil or other metal foil, Materials and laminated materials can be suitably used.

The lamination method of the sheet-like base material, the lamination method of the sheet-like base material and the heat seal layer and the like are not limited. For example, a known method such as a dry lamination method, an extrusion lamination method, a wet laminate method and a heat lamination method have.

The thickness of the sheet-like base material is not particularly limited, but a range used in a known packaging material can be set. For example, it is preferable that the thickness is usually about 1 to 500 mu m.

The heat seal layer 32 is disposed on the outermost layer (the outermost surface) of the layered body 34. [ As the heat seal layer 32, a well-known heat seal layer can be employed. For example, a layer formed by an adhesive such as a lacquer type adhesive, an easy peel adhesive, or a hot melt adhesive other than a known sealant film can be employed.

The main component of the heat seal layer is not limited, and can be the same as the main component of the heat seal agent shown above. More specifically, it is preferable to use a low density polyethylene, medium density polyethylene, high density polyethylene, linear (low density) polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ionomer resin, ethylene- A polyolefin resin such as ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene-propylene copolymer, methylpentene polymer, polybutene polymer, polyethylene or polypropylene is dissolved in a solvent such as acrylic acid, methacrylic acid, Acid-modified polyolefin resins modified with unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid, polyvinyl acetate resins, poly (meth) acrylic resins, polyacrylonitrile resins, polyvinyl chloride resins, In addition to the resin, A copolymer containing a combination of monomers constituting these, a modified resin, and the like can be used. As a constitution of the heat seal layer, a sealant film of a single layer can be used, and a sealant film of two or more layers laminated by coextrusion or extrusion can be used.

The thickness of the heat seal layer is not particularly limited, but is preferably about 1 to 100 mu m, more preferably about 3 to 50 mu m, from the viewpoints of productivity and cost. In the packaging material of the present invention, in the heat seal, a part or all of the coating film existing on the area to be heat-sealed is buried in the heat seal layer, and the heat seal layer can be formed as the outermost surface. Therefore, it is preferable to set the thickness of the coating film so as to be as large as possible in the heat seal layer within the above-mentioned thickness range.

In the laminate 34, various properties (moisture permeation resistance (moisture resistance permeability), oxygen permeability (oxygen resistance permeability), light shielding property The layers employed in known packaging materials may be laminated at arbitrary positions for the purpose of imparting heat resistance (light shielding property), heat insulation property, impact resistance, and the like). For example, a printing layer, a printing protective layer (so-called OP layer), a colored layer, an adhesive layer, an adhesive reinforcing layer, a primer coating layer, an anchor coating layer, a lubricant layer, a lubricant layer and an antifogging agent layer have.

b) Formation of a coating film on the surface of the laminate

In the packaging material of the present invention, by forming the coating film of the present invention on the surface of the heat seal layer of the laminate, excellent water repellency and oil repellency are exhibited. That is, it is particularly preferable to form the coating film of the present invention adjacent to the heat seal layer.

The deposition amount (weight after drying) of the coating film formed on the surface of the laminate is not limited, but can be suitably set within a range of generally 0.01 to 30 g / m ² , preferably 0.1 to 30 g / m ² . By setting the content within the above range, more excellent water repellency and oil repellency can be obtained over a long period of time. Thus, for example the range of 0.01~10g / m ^2, in particular the range of 0.2~1.5g / m ^2, may also be set in the range of 0.2~1g / m ^2.

In the present invention, the coating film preferably has a porous layer, and its thickness is preferably about 0.1 to 5 mu m, more preferably about 0.2 to 2.5 mu m. By attaching in such a porous layer state, it is possible to include a large amount of air in the layer, and more excellent water repellency and oil repellency can be exhibited.

Also in the packaging material of the present invention, it is preferable that the surface of the coating film has a concavo-convex structure in which the metal oxide composite particles are continuously formed. Whereby more excellent water repellency and oil repellency can be achieved.

The coating film may be formed on the entire surface of the heat seal layer side (the entire surface opposite to the sheet-like substrate side) or may be formed in an area other than a heat-sealable area (so-called adhesion area).

According to the present invention, even when adhered to the entire surface of the heat seal layer, the heat seal is not substantially inhibited because part or all of the coating film existing on the heat seal area is buried in the heat seal layer, It is preferable that the heat seal layer is attached to the entire surface of the heat seal layer.

The packaging material 31 can be suitably manufactured by, for example, the following method. That is, a method for producing a packaging material comprising a sheet-like base material and a heat seal layer, the method comprising the steps of: forming a heat seal layer on the outermost surface of the heat seal layer in the laminate having the heat- And a step of forming a coating film (coating film forming step) by applying a dispersion liquid containing metal oxide composite particles in a solvent to all of them.

In the coating film forming step, a part or all of the outermost surface of the heat seal layer in the laminate including the sheet-like base material and the heat seal layer and the heat seal layer as the outermost layer is coated with a metal oxide composite particle A coating film is formed by applying a dispersion liquid.

As the laminate, those described in the above a) may be used. Therefore, the sheet-shaped base material, the heat seal layer, and other layers may be formed as described above.

As the dispersion liquid, a dispersion in which at least a metal oxide composite particle (powder) is dispersed is used. The metal oxide composite particle in this case may be the one described in the above-mentioned " 1-1) metal oxide composite particle ".

The solvent is not particularly limited as long as it does not deteriorate the metal oxide composite particle to be used, and examples thereof include alcohols (ethanol), cyclohexane, toluene, acetone, IPA, propylene glycol, hexylene glycol, butyldiglycol, Glycol, n-pentane, n-hexane, hexyl alcohol and the like. The dispersion amount of the metal oxide composite particles relative to the solvent is not limited, and can be set at, for example, about 10 to 200 g / L. Therefore, it can be adjusted within a range of 10 to 100 g / L, for example.

Further, in the present invention, other additives may be appropriately added to the dispersion liquid as needed within a range not hindering the effect of the present invention. For example, a dispersing agent, a colorant, an anti-settling agent, a viscosity adjusting agent and the like. As described above, powder of an adhesive (particularly, a heat seal agent) may be dispersed in the dispersion to further increase the adhesive force of the coated film.

As a coating method in the case of applying the dispersion liquid, any known methods such as roll coating, gravure coating, bar coating, doctor blade coating, comma coater, part coat, and brush coating may all be employed. For example, when a roll coating or the like is employed, a coating process can be carried out by forming a coating film on the heat seal layer using a dispersion containing at least a metal oxide composite particle dispersed in a solvent.

After the coating film forming step, a step of drying the coating film may be performed prior to the heating step. The drying method may be either natural drying or forced (heating) drying. In the case of heating and drying, the temperature is usually 200 占 폚 or lower, preferably 100 占 폚 or lower.

In the present invention, after the dispersion liquid is coated on the surface of the material, a heat treatment step may be performed after the drying step or in place of the drying step. In particular, in the case where the dispersion contains a heat sealant as an adhesive component, the heat seal agent is melted by heat treatment of the coating film on the surface of the material, so that the coating film can be firmly fixed to the surface of the material. As a result, it is possible to form a coating film in which peeling and dropout are less likely to occur. The heat treatment temperature may be appropriately set according to the type of the heat seal agent to be used, etc., but it is usually within a range of about 150 to 250 캜. The atmosphere of the heat treatment is not limited, but it may be usually in the air or in an oxidizing atmosphere.

The packaging material thus obtained can be used as it is or after being processed. As the processing method, the same method as in the case of known packaging materials can be adopted. For example, emboss processing, half cut processing, notch processing, and the like may be performed. The packaging material of the present invention can be suitably used for a lid material, for example, a mortar such as a molded container, a wrapping paper, a tray, a tube and a bag or a pouch.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited to the embodiments.

Example 1-1

(1) Preparation of metal oxide composite particles

100 g of a vapor phase silica powder (product name: "AEROSIL 200" manufactured by Nippon Aerosil Co., Ltd.) having an average primary particle diameter of 12 nm and a BET specific surface area of 200 m ² / g was placed in a reaction vessel, 500 g of a commercially available surface treatment agent was sprayed while stirring in an atmosphere, followed by stirring at 200 캜 for 30 minutes and then cooling. Thus, powders of surface-modified silica fine particles (surface modified silica fine particles) (metal oxide composite fine particles) were obtained. As the above-mentioned treatment agent, there may be used a copolymer of polyfluoroctyl methacrylate, 2-N, N-diethylaminoethyl methacrylate, 2-hydroxyethyl methacrylate and 2,2'-ethylenedioxy ethyl dimethacrylate An aqueous dispersion of the copolymer (solid concentration: 20% by weight) was used. Table 1 shows the carbon content and the fluorine content of the obtained surface-modified silica fine particles (powder).

(2) Preparation of dispersion

30 parts by weight of the surface-modified silica fine particles obtained in the above (1) were added to and mixed with 200 parts by weight of ethanol to prepare a dispersion.

(3) Formation of coating film

A laminate of polyethylene telephthalate (thickness 12 占 퐉) / polyurethane dry laminate adhesive / aluminum foil 20 占 퐉 / polyurethane dry laminate adhesive / (polyethylene / polypropylene) coextruded film was used, The sample (packaging material) of Example 1-1 was prepared by applying the dispersion prepared in (2) above to a coating amount after drying of 3 g / m ² using a bar coater on the surface and then heating it in an oven at 180 캜 for 15 seconds. ≪ / RTI >

Examples 1-2

A sample (packaging material) was prepared in the same manner as in Example 1-1 except that 500 g of the surface treating agent was changed to 300 g. Table 1 shows the carbon content and the fluorine content of the obtained surface-modified silica fine particles (powder).

Example 1-3

A sample was prepared in the same manner as in Example 1-1 except that 500 g of the surface treatment agent was changed to 800 g. Table 1 shows the carbon content and the fluorine content of the obtained surface-modified silica fine particles (powder).

Examples 1-4

A vapor-phase silica powder (product name: "AEROSIL 50" manufactured by Nippon Aerosil Co., Ltd.) having an average primary particle diameter of 30 nm and a BET specific surface area of 50 m ² / g was used as the metal oxide particles, and 500 g of the surface treatment agent was changed to 25 g (Packing material) was produced in the same manner as in Example 1-1. Table 1 shows the carbon content and the fluorine content of the obtained surface-modified silica fine particles (powder).

Examples 1-5

(Product name: "AEROSIL 50" manufactured by Nippon Aerosil Co., Ltd.) having an average primary particle size of 30 nm and a BET specific surface area of 50 m ² / g was used as the metal oxide particles. A sample (packaging material) was similarly prepared. Table 1 shows the carbon content and the fluorine content of the obtained surface-modified silica fine particles (powder).

Examples 1-6

A vapor-phase silica powder (product name: AEROSIL 300 manufactured by Nippon Aerosil Co., Ltd.) having an average primary particle size of 7 nm and a BET specific surface area of 300 m ² / g was used as the metal oxide particles, and 500 g of the surface treatment agent was changed to 750 g (Packing material) was produced in the same manner as in Example 1-1. Table 1 shows the carbon content and the fluorine content of the obtained surface-modified silica fine particles (powder).

Comparative Example 1-1

A sample was prepared in the same manner as in Example 1-1 except that the amount of the surface treating agent was changed to 500 g. Table 1 shows the carbon content and the fluorine content of the obtained surface-modified silica fine particles (powder).

Comparative Example 1-2

A sample (packaging material) was prepared in the same manner as in Example 1-1, except that 100 g of trifluoropropyl trimethoxysilane was used as the treating agent. Table 1 shows the carbon content and the fluorine content of the obtained surface-modified silica fine particles (powder).

Example 2-1

30 parts by weight of surface-modified silica fine particles and 30 parts by weight of a commercially available heat seal agent (100 parts by weight of a polypropylene-based heat sealable dispersion (solid content: 18% by weight, the same applies hereinafter) ) Was added to and mixed with 200 parts by weight of an organic solvent (toluene) to prepare a dispersion. A sample (packaging material) was produced in the same manner as in Example 1-1 except that the thus obtained dispersion was used.

Example 2-2

30 parts by weight of the surface-modified silica fine particles and 200 parts by weight of a commercially available heat seal agent (100 parts by weight of the polypropylene-based heat sealable dispersion) in the "(2) Preparation of the dispersion liquid" Followed by mixing and mixing. A sample (packaging material) was produced in the same manner as in Example 1-2 except that the thus obtained dispersion was used.

Example 2-3

30 parts by weight of the surface-modified silica fine particles and 200 parts by weight of a commercially available heat sealant (100 parts by weight of the polypropylene-based heat sealable dispersion) in the "(2) preparation of dispersion" Followed by mixing and mixing. A sample (packaging material) was produced in the same manner as in Example 1-3 except that the thus obtained dispersion was used.

Examples 2-4

30 parts by weight of the surface-modified silica fine particles and 200 parts by weight of a commercially available heat sealant (100 parts by weight of the polypropylene-based heat sealable dispersion) in the "preparation of (2) Followed by mixing and mixing. A sample (packaging material) was produced in the same manner as in Example 1-4 except that the thus obtained dispersion was used.

Example 2-5

30 parts by weight of the surface-modified silica fine particles and 200 parts by weight of a commercially available heat sealant (100 parts by weight of the polypropylene-based heat sealable dispersion) in the "(2) Preparation of dispersion liquid" Followed by mixing and mixing. A sample (packaging material) was produced in the same manner as in Example 1-5 except that the thus obtained dispersion was used.

Examples 2-6

30 parts by weight of the surface-modified silica fine particles and 200 parts by weight of a commercially available heat sealant (100 parts by weight of the polypropylene-based heat sealable dispersion) in the "(2) Preparation of dispersion" of Example 1-6 Followed by mixing and mixing. A sample (packaging material) was produced in the same manner as in Example 1-6 except that the thus obtained dispersion was used.

Comparative Example 2-1

30 parts by weight of the surface-modified silica fine particles and 200 parts by weight of a commercially available heat sealant (100 parts by weight of the polypropylene-based heat sealable dispersion) in the "(2) Preparation of the dispersion liquid" Followed by mixing and mixing. A sample (packaging material) was produced in the same manner as in Comparative Example 1-1 except that the thus obtained dispersion was used.

Comparative Example 2-2

30 parts by weight of the surface-modified silica fine particles and 200 parts by weight of a commercially available heat sealant (100 parts by weight of the polypropylene-based heat sealable dispersion) were added to 200 parts by weight of an organic solvent (toluene) in "(2) Followed by mixing and mixing. A sample (packaging material) was produced in the same manner as in Comparative Example 1-2 except that the dispersion thus obtained was used.

Test Example 1 (Oil-repellent)

The oil-repellency (25 占 폚) was examined on the samples obtained in Examples and Comparative Examples. Specifically, the state of the droplets (droplets) was observed by dropwise adding a few drops of olive oil, with the water-repellent / oil-imparting surface of each sample being the test surface. As the olive oil, commercially available product "AJINOMOTO olive oil" (edible olive oil, viscosity: 0.9 dPa 揃 s (20 째 C)) (manufactured by Ajinomoto of Japan) was used. The evaluation was made as "o" indicating that the oil repellency was exhibited (rolling in the form of beads), and "x" indicating that the oil repellency was not seen (not rolling in the wet state). The results are shown in Tables 1 and 2.

Test Example 2 (Contact angle)

The contact angles (25 DEG C) were measured on the samples obtained in Examples and Comparative Examples. Specifically, the water-repellent / oil-imparting surface of each sample was used as a test surface, and a contact angle measuring apparatus (a liquid interface analyzer "Drop Master 300", Kyowa Interface Science Co., Ltd. ) Was used to measure the contact angle of pure water and olive oil (about 2-4 [mu] l). The measurement results are shown in N number of 5 circuits, and the average value of the contact angles is shown as a result. As the olive oil, a commercially available product "AJINOMOTO OLIVE OIL" (edible olive oil) (manufactured by Ajinomoto Co., Ltd., Japan) was used. The results are shown in Tables 1 and 2.

Test Example 3 (falling angle)

The fall angles (25 DEG C) of the samples obtained in Examples and Comparative Examples were measured. Specifically, the water-repellent / oil-imparting surface of each sample is used as a test surface, and this surface is used as an upper surface, which is fixed on a horizontal plane with a clip. Olive oil is dropped at a very short distance to tilt the horizontal plane And the angle at which the olive oil started to flow was observed. As the olive oil, a commercially available product "AJINOMOTO OLIVE OIL" (edible olive oil) (manufactured by Ajinomoto Co., Ltd., Japan) was used. The results are shown in Tables 1 and 2.

Test Example 4 (Abrasion resistance)

The durability (abrasion resistance) of the samples obtained in Examples and Comparative Examples was examined. The test method was carried out in accordance with the JIS standard "JIS L0849". Concretely, the water-repellent / oil-imparting surface of each sample was used as a test surface, and a wear test was conducted by a friction tester (product of SHOWA JUKI, Japan), and it was confirmed whether or not the oil repellency was maintained in the olive oil Respectively. As a condition, a dry cloth was attached to the tip of the rubbing member, and the test surface was subjected to reciprocating rubbing 100 times at a reciprocating speed of 30 times per minute at a load of 2N. As the olive oil, a commercially available product "AJINOMOTO OLIVE OIL" (edible olive oil) (manufactured by Ajinomoto Co., Ltd., Japan) was used. In the evaluation, the case where oil repellency was maintained on the same basis as in Test Example 1 was defined as " ", and the case where oil repellency was lost was evaluated as " X ". The results are shown in Tables 1 and 2.

Test Example 5 (Heat Sealing Test)

The samples obtained in Examples 2-1 to 2-6 and Comparative Examples 2-1 to 2-2 were examined for heat sealability. Specifically, a lid member (90 mm x 90 mm square) was cut out from each package material sample, and then a container made of polypropylene with flange (flange width 3.5 mm, flange outer diameter 75 mm x inner diameter 68 mm, 68 mm, inner volume about 155 cm ³ ), and the lid material was heat-sealed to fabricate a package. The conditions of the heat seal were tightly sealed for 1.0 ^second at a temperature of 200 占 폚 and a pressure of 3 kgf / cm2. The tabs of the lid material on each of the sealed packages were pulled out at a speed of 100 mm / min in the direction of an elevation angle of 45 degrees when viewed from the opening, and the maximum load (N) at the initial stage of opening was measured. The results are shown in Table 2.

As apparent from these results, the coating film of the embodiment comprising the metal oxide composite particles (surface-modified silica fine particles) coated with the coating layer made of the polyfluoroalkyl methacrylate resin having the predetermined coating amount, It can be seen that excellent water repellency and oil repellency can be exerted.

11: metal oxide composite particle
12:
13: metal oxide particles (agglomerate)
21: Coating film
22: Material
23: Pore
24: Coating film surface
31: Packing material
32: Heat seal layer
33: sheet-like substrate
34:

Claims (14)

As a coating film (coating film) formed on the surface of a material for imparting water repellency and oil repellency,
(1) The coating film contains metal oxide composite particles,
(2) The metal oxide composite particle includes a coating layer (coating layer) comprising a) metal oxide particles and b) a polyfluoroalkyl methacrylate resin formed on the surface thereof,
(3) the value obtained by dividing the fluorine content (wt%) of the metal oxide composite particle by the surface area (surface area) (m ² / g) of the metal oxide particle is 0.025 to 0.180 ,
(4) a void formed between the metal oxide composite particles,
(5) The coating film may further comprise a heat seal agent,
(6) The coating film is obtained by coating a surface of a material with a dispersion liquid in which at least metal oxide composite particles and particles of a heat seal agent are dispersed in a solvent, and then performing a drying step and / or a heat treatment step. Oily coating film.
The method according to claim 1,
Wherein the value obtained by dividing the carbon content (% by weight) of the metal oxide composite particle by the surface area (m ² / g) of the metal oxide particle is 0.05 to 0.400.
3. The method according to claim 1 or 2,
Water repellent coating film having an average primary particle diameter of 5 to 50 nm of the metal oxide particles.
The method according to claim 1 ,
Wherein the metal oxide particles are at least one of silicon oxide particles, aluminum oxide particles, and titanium oxide particles.
The method according to claim 1 ,
Wherein the coating layer contains no silicon component.
The method according to claim 1 ,
A water-repellent / oil-repellent coating film in which the coating film is porous.
The method according to claim 1 ,
A water-repellent / oil-repellent coating film comprising a concavo-convex structure (concavo-convex structure) formed by metal oxide composite particles, the surface of the coating film being the outermost surface.
The method according to claim 1 ,
Wherein the content of the metal oxide composite particles in the coating film is 10 to 100% by weight.
delete A packaging material (packaging material) comprising the water- and oil-repellent coating film of claim 1 .
A packaging material comprising the water- and oil-repellent coating film, the heat seal layer and the substrate layer (substrate layer) of claim 1 sequentially.
12. The method of claim 11,
A packaging material in which a part or all of a water- and oil-repellent coating film existing on a region to be a heat seal is embedded in a heat seal layer at the time of heat sealing. The method according to claim 1,
A water-repellent and oil-repellent coating film comprising a void formed by continuous contiguous metal oxide composite particles and a surface having a concavo-convex structure formed by the particle body.
A method for producing a coating film formed on a surface of a material for imparting water repellency and oil repellency,
A dispersion liquid obtained by dispersing at least metal oxide composite particles and heat sealable particles in a solvent is coated on the surface of the material, and then a drying step and / or a heat treatment step is performed,
Wherein the metal oxide composite particle comprises a) a metal oxide particle, and b) a coating layer comprising a polyfluoroalkyl methacrylate resin formed on the surface thereof,
Wherein the value obtained by dividing the fluorine content (wt%) of the metal oxide composite particle by the surface area (m ² / g) of the metal oxide particle is 0.025 to 0.180.

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